Method of testing glass fiber coating compositions

ABSTRACT

A method of forming a continuous film of an elastomeric latex and a phenolic resin comprising spraying a plurality of coats of the aqueous admixture onto a nonadherent surface. The nonadherent surface is at a temperature of 120 DEG  F. or greater and each coat of the aqueous admixture is less than about 0.7 mil dry film thickness. The film so formed can be tested for physical properties and the testing results are capable of being correlated with the performance of glass fibers with the aqueous admixture coated thereon for reinforcement of elastomeric matrices.

REFERENCE TO CROSS-RELATED APPLICATIONS

This is a divisional of application Ser. No. 587,471, filed June 16,1975, which is a continuation of application Ser. No. 475,705, filedJune 3, 1974, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a method of forming a continuous film from anaqueous admixture of an elastomeric latex and a phenolic resin.

It has long been recognized that glass fiber material makes an idealreinforcement for rubber products such as automobile tires, powertransmission belts and the like. In preparing glass fiber material forsuch applications, the individual glass fibers or groups of glass fibersin the form of strand, rope, cord, roving, fabric and the like arecoated with a rubber adhesive to aid in bonding the glass to theelastomeric materials to be reinforced. The rubber adhesive generallycomprises a resin and an elastomeric material to form a bond between theglass and the main body of material being reinforced.

Generally, in the production of fiber glass reinforcing cords or otherbundle forms, individual fibers are coated with a sizing and then thefibers are brought together in bundle form. Commonly the sizing containsa coupling agent such as a silane, a lubricant or other ingredients toassist in the handling of the bundle during processing. The bundle isthen coated by dipping or otherwise contacting it with a coating mixturecontaining an elastomeric latex and ahomogeneous resinous component.

The term "elastomer" as used herein in intended to mean and include bothsynthetic and natural rubber. "Natural rubber" as used herein is theelastic solid obtained from the sap or latex of the Hevea tree, themajor constituent being the homopolymer of 2-methyl 1,3-butadiene(isoprene). "Synthetic rubber" as used herein is meant to encompasspolymers based upon at least 2 percent of a conjugated unsaturatedmonomer. The conjugation being in the 1,3 position in the monomer chainand the final monomer in its uncured state having an extensibility of atleast 200 percent and a memory of at least 90 percent when stretchedwithin the extensibility limits and released instantaneously. Theconjugated unsaturated monomers which are used in the preparation ofsynthetic rubbers are, but not limited to, chloroprene, butadiene,isoprene, cyclopentadiene, dicyclopentadiene and the like. Other olefinscapable of free radical anionic or cationic interpolymerization into thepolymer chain with the conjugated unsaturated monomer are useful informing synthetic rubbers. These olefins are typically monoethylenicallyunsaturated monomers. "Monoethylenically unsaturated" as used herein ischaracterized by the monomer having one CH₂ ═ C < group. Thesemonoethylenically unsaturated monomers are, but not limited to, theacrylic monomers such as methyacrylic acid, acrylic acid, acrylonitrile,methyacrylonitrile, methylacrylate, methylmethacrylate, ethylacrylate,ethylmethacrylate and the like. Monoolefinic hydrocarbons such asethylene, butylene, propylene, styrene, alphamethylstyrene and the likeand other functional mono unsaturated monomers such as vinyl pyridine,vinyl pyrrolidone and the like functional vinylic monomers.

Glass fibers are excellent reinforcing materials and are distinguishablefrom other fibrous reinforcing materials such as natural and syntheticorganic fibers in that the glass fibers do not become elongated ordeformed under stress to the extent that other fibers do. Unlike otherfibers, particular combinations of glass fibers with encapsulatingcoatings cooperate to yield reinforcing materials that have greatertensile strength than either the glass or coating material alone. Whileother materials which are subject to substantial stress elongation areessentially limited in tensile strength to the basic strength of thebare fibers, even if coated, properly coated glass fibers have greaterstrength than the glass alone. For example, the low modulus ofelasticity of glass may be exploited to provide reinforced tires havingsuperior road performance if an appropriate coating medium is providedto transfer stresses to all fibers in the glass fiber cord so thatloading throughout is substantially uniform. This phenomena isillustrated by the observation that a typical uncoated glass fiber cord[G-75, 5/0, filament count 2,000, i.e, 2,000 filament strands of Gfibers, (about 3.7 × 10⁻⁵ inches diameter), 7,500 yards per pound ofglass] has a tensile strength of about 35 to 40 pounds by ASTM TestD578-52. This same cord when coated with an elastomerresorcinol-formaldehyde coating has a tensile strength of about 50 to 70pounds.

A plurality of components are used in the coating composition for theglass fibers to impart various properties thereto. Among thesecomponents are elastomers, as previously described, and phenolic resinsespecially resorcinol-formaldehyde resins. Further, carboxylatedpolymers are sometimes added to the dip material to impart adhesion andimprove tensile strength. Waxes are sometimes added to the dipformulation to provide stability to ultraviolet light. Due to theplurality of components used in coating compositions which determine thefinal properties of the cord, a great deal of formulation must beconducted in order to find an acceptable or improved coating compositionfor the glass fiber cord.

Because there are so many components and the extent of the interactionof the ratios and compositions of these components is not completelyknown, physical testing of the tire cord is necessary in order todetermine if a product is acceptable for final use.

Testing methods of the cord are conducted both in the laboratory and inthe field. Laboratory testing is composed of both the testing of thecord itself and the testing of the cord embedded in a rubber matrix. Thenormal testing of the cord itself is usually by a tensile strengthmeasurement. When the cord is embedded in a rubber matrix the compositeis tested for its flexibility in accordance with the Scott flex test.The Scott flex test involves taking strips of rubber cord composite andflexing this composite for the desired number of cycles. After thecycles have been completed, the composite is inspected for breakage ofglass filaments. This test is used as an indication of how the glassfiber cord will perform in its final use, i.e., tires, or powertransmission belts.

In testing the adhesion of the cord to a rubber matrix the cord isembedded in the rubber matrix and sectioned so that the interface of thecord and the rubber matrix can be pulled in opposite directions in anInstron.sup.® testing device. This test for adhesion is also consideredto be indicative of how the cord will perform in its final application.

Although these laboratory tests have been found to be somewhatrepresentative of the quality of the glass fiber cord, these testingmethods are not always reliable in predicting the final performance ofthe glass fiber cord. Therefore, field testing of the cord in tires andin power transmission belts must be made.

In order to field test the cord, it must be used in the construction ofa tire. Therefore, individual tires having the cords to be tested arefabricated and run through various destructive testing techniques suchas riding a car with the tires to be tested over a course ofcobblestones for a certain number of miles; running the tires to betested at high speed and low speed and finally after the predeterminedamount of driving time has been completed, the tires are X-rayed andinspected for broken filaments in the cord.

The laboratory testing techniques do not involve great expense in bothtime and materials; however, the field testing of the tires which is thetrue indication of the performance of the cord amounts to a great dealof cost due to the expense in building the tires and testing the tires.It has been hypothesized by workers in this area that if the physicalproperties of the glass fiber coating formulation could be determined,an indication of the final properties of the tires could be obtained.However, the continuous, uniform, free films of the coating compositionhave not heretofore been able to be produced. This is attributable tothe fact that when the coating composition as such is coated on asubstrate, in a film thickness acceptable for testing, on drying thefilm cracks and becomes discontinuous or forms a powder; therefore,losing all utility for any type of testing technique.

The instant invention provides a method of forming a uniform continuous,free film of adequate thickness to test the physical characteristics ofthe elastomeric latex-phenolic resin admixture in its cured state.

SUMMARY OF THE INVENTION

A process for forming a continuous film from an aqueous admixture of anelastomeric latex and a phenolic resin comprises spraying the admixtureonto a surface being heated to a temperature of greater than 120° F. Asufficient amount of the admixture is sprayed onto the surface to form abase coat film of less than about 0.7 mil. Subsequent coats of theadmixture are sprayed onto the base coat to impart a coating thicknessof less than 0.7 mil per coat to form a uniform final film of greaterthan about 4 mils. The heated surface is composed of a nonadhesivematerial such as Teflon.sup.® floropolymer or the like so that the filmcan be easily removed from the heated surface.

As previously discussed, a broad range of elastomeric latices have beenused to form the strands, yarns and cords which are characterized asglass fiber bundles. Particular elastomeric latices suited for use inthis invention include styrene-butadiene-vinylpyridine terpolymers,neoprene, polyisoprene, butyl rubber, butadiene-styrene copolymers(styrene-butadiene-rubber) acrylonitrile-butadiene-vinylpyridineterpolymers and the like.

Useful resins employed in this invention include resorcinol-formaldehyderesins, phenol-formaldehyde resins and the like. Both the resole andnovolac type phenolic aldehyde resins have been found to be useful informing the rubber adhesive coating composition. The resole resins arecharacterized by the formation of the resin induced by base catalysisand the novolac resins are characterized by their formation by acidcatalysis. Generally, the resole reins are more highly methylolated thanthe novolacs. The choice between the resole or novolac resin in therubber adhesive coating composition is contingent on the other materialsused in the coating composition itself and the desired properties of thefinal glass fiber bundle. Rubber adhesive systems which are useful inthe practice of the invention include those disclosed in U.S. Pat. Nos.2,691,614; 2,817,616 and 2,822,311 which are incorporated herein byreference and made a part hereof.

Other materials may be included in the coating composition which impartthe desired properties to the final coated cord. These materials aretypically silicone coupling agents, waxes and like additives.

Typical silicone coupling agents are, but not limited to, the aminosilane coupling agents, such as gamma-aminopropyltriethoxysilane, N-betaaminoethyl gamma-aminopropyltrimethoxysilane and the like. Otherfunctional silanes may also be utilized such as vinylbeta-methoxyethoxysilane, gamma-glycidoxypropyltrimethoxysilane,vinyltriacetoxysilane and the like.

In the principle of the invention, the heated substrate has atemperature greater than 120° F. so that the volatile components of thecoating composition are substantially removed from the coatingcomposition as they are coated on the substrate. In order thatsubstantially all of the volatiles are removed, the base film ispreferably less than about 0.7 mil to aid in evaporation of thevolatiles. If the final film thickness of a single coat is greater than0.7 mil, cracking and discontinuity of the film will occur and itsutility as a testing specimen will be impaired if not completelydestroyed.

The final film immediately before removal from the heated substrate issubstantially water free. "Substantially water free" as used hereinmeans that the film contains less than 5 percent by weight water and isgreater than 94 percent by weight solid content.

It is preferred that the temperature of the heated surface be below thetemperature of curing of the coating composition. This allows the curingof the film to be conducted at a separate stage and under processingconditions which will more adequately approximate the curing of thecoated cord during commercial processing.

It has been determined that representative film thicknesses of 4 mils orgreater are necessary to adequately predict the final properties of aparticular coating composition on the glass fiber cord, and morepreferably, final film thicknesses of 4 to 23 mils most closelyapproximate the performance of the cord in their final use.

The invention will be further elucidated by the following embodiments.

DESCRIPTION OF PREFERRED EMBODIMENTS

The coating admixtures useful in forming the films of the invention havethe following typical composition:

    ______________________________________                                                               Range in Parts                                         Ingredient             By Weight                                              ______________________________________                                        Elastomeric latex, 40 - 60 percent                                                                   150 - 380                                              solids in water                                                               Water                   60 - 110                                              NH.sub.4 OH            0.2 - 1                                                Phenolic resin, 50 - 90 percent                                                                       6 - 28                                                solids in water                                                               Formaldehyde (37 percent)                                                                             2.5 - 14.5                                            Water                  1.0 - 8.0                                              Wax                     0 - 52                                                ______________________________________                                    

The admixtures are prepared by adding the larger volume of water to anagitating premix tank followed by the addition of ammonium hydroxide.The phenolic resin is added to this mixture with continuing stirringuntil complete dissolution of the resin occurs. The elastomeric latex isadded to a batch tank and to it is added the contents of the premix tankwith stirring which is continued for about five minutes after theaddition of the premix. The formaldehyde is added to the mixture and themixture is stirred for about ten minutes. A solution of the wax is addedwith agitation. This coating mixture is allowed to age for at least twohours before use.

The wax component of the formulation is typically a microcrystalline waxor a paraffin wax. The microcrystalline wax has a melting point of atleast 100° C. and preferably 135° C. The paraffin wax has a preferredmelting range of 50° C. to 90° C. Other waxes known to those skilled inthe art may be utilized in forming the coating compositions of theinvention.

A Teflon.sup.® floropolymer (manufactured by du Pont) coated steel hotplate cover is placed over a variable temperature hot plate which ispreheated so that the temperature of the Teflon.sup.® floropolymersurface is greater than 120° F. but below the curing temperature of thecoating composition. The edges of the hot plate cover are masked usingmasking tape with an underlying disposable protective surface to preventoverspray onto the hot plate other than the Teflon.sup.® floropolymercoated area. An air pressurized spray gun is utilized in spraying thecoating composition. It has been found that a spraying pressure of about40 pounds per square inch with a setting on the spray gun for a finespray, forms an excellent film.

A uniform base coat of the coating composition covering the hot platecover is considered as one pass, with each subsequent pass addingthickness to the film. The path of the gun on each pass is at 90° tothat of the preceding pass, thereby eliminating the possibility ofnonuniformity of film thickness which occurs by subsequent coats beingapplied at the same direction as the previous coats. The thickness ofthe sample or the final dry coating composition depends upon the percentsolids of the dip and the setting of the gun. Typically, nine passeswith the spray gun across the hot plate cover will produce a 5 mil dryfilm and 40 passes with the spray gun across the hot plate cover willproduce a film of about 20 mils when the spray gun is set for fine sprayand the coating composition is at about 27 to 35 percent by weightsolids.

After the last coat of the coating composition is applied to thesubstrate, the film is stripped from the Teflon.sup.® floropolymercoated hot plate after substantially all of the water is removedtherefrom and placed in a heated press at or above the curingtemperature of the coating compositions solids, approximately 300° F. Acuring time of 1 to 2 minutes and a pressure of 1,000 pounds per squareinch is adequate to cure the coating composition solids. The film isremoved from the press and is ready for testing after cooling to roomtemperature.

EXAMPLE I

A Teflon²⁰⁰ floropolymer coated, steel hot plate cover is placed over aLindburg variable temperature hot plate. The hot plate is preheated sothat the temperature of the Teflon.sup.® floropolymer surface is about120° F. The edges of the cover are masked using masking tape with anunderlying disposable protective surface to prevent overspray onto thehot plate other than the Teflon.sup.® floropolymer coated area.

A Binks Model 18, one quart spray gun is utilized in spraying thecoating composition. The air pressure utilized in spraying is 40 poundsper square inch and the setting on the spray gun is for a fine spray. Acoating composition having the following ingredients is charged to thereserve tank of the spray gun:

    ______________________________________                                        Ingredient               Parts by Weight                                      ______________________________________                                        Gentac ® Latex 121 (Styrene:                                                                       244                                                  butadiene: vinylpyridine, 15.5:73.5:11,                                       41 percent solids in water)                                                   Water                    89                                                   Penacolite ® Resin (resorcinol-formal-                                                             15.7                                                 dehyde novolac resin, 0.6 formaldehyde: 1                                     resorcinol, 70 percent solids in water)                                       Ammonia (28 percent in water)                                                                          0.5                                                  Formalin (37 percent formaldehyde)                                                                     6.75                                                 Water                    4.0                                                  Mobilcer ® Q wax (microcrystalline wax                                                             10                                                   50 percent solids in water)                                                   32 percent solids content                                                     ______________________________________                                    

A uniform base coat of coating composition covering the entire hot platewas considered as one pass being sprayed on the hot plate cover witheach subsequent pass adding thickness to the sample. The course of thegun on each pass is at 90° to that of the preceding pass therebyeliminating the possibility of nonuniformity of film thickness whichoccurs by subsequent coats being applied at the same direction asprevious coats. Nine coats of substantially equal thickness of thecoating admixture were sprayed onto the hot plate cover.

After coating, the film was allowed to dry until tack free on the hotplate cover. After drying the sample film was stripped from the hotplate cover. The free film was smooth and continuous. The film wasplaced in a mold and cured at 1000 pounds per square inch for 1 minute.

Three samples as produced above were made which had an average filmthickness of 4 to 7 mils.

EXAMPLES II-V

Four coating admixtures were prepared in accordance with Example Iexcept that the amount of Penacolite.sup.® resin was varied. Thefollowing table represents the variation of phenolic resin in theseexamples:

    ______________________________________                                        Example Phenolic Resin (Penacolite ® Resin) Level                         ______________________________________                                         II     11.4 parts                                                            III     19.8 parts                                                             IV     24.2 parts                                                            V       28.6 parts                                                            ______________________________________                                    

Films of each of the admixtures were produced in accordance with theprocedure of Example I and tested for tensile strength, percentelongation and 10 percent modulus.

Tensile strengths of the films were tested as follows. Three sampleswere cut from each of the films of Examples I through V. The samples hadthe dimensions of 4 inches by 0.25 inch and a thickness between 4 and 7mils. One end of the sample was placed in one jaw of an Istron.sup.®test device while the opposite end was placed in another jaw of the testdevice. The test span was 1.25 inches with a pull rate of two inches perminute. The jaws of the test instrument were traveled in oppositedirections until the sample separated. At the point of separation, theforce required to obtain separation was recorded. Three samples of eachfilm of Examples I through V was tested. The tensile strengths asobtained above for each example were averaged. The average tensilestrength of the films of the examples is recorded on Table 1.

Percent elongation was run by the same method as tensile strength, onlyat the point of sample separation the distance between the Instron.sup.®jaws was recorded. From this value was substracted the original lengthof the sample, and percent elongation was calculated. The averagepercent elongation for the films of each example are reported in Table1.

Ten percent modulus was run by the same method as both tensile strengthand elongation except that the samples were elongated 10 percent oftheir original length and the force required to elongate the samples wasrecorded.

                  Table 1                                                         ______________________________________                                               Dip                           10 Percent                                      Composition Tensile   Percent Modulus                                  Example                                                                              Parts Resin P.S.I.    Elongation                                                                            P.S.I.                                   ______________________________________                                        I      11          1269      26.5    1033                                     II      8           790      29.12    627                                     III    14          1456      19.6    1334                                     IV     17          1865      12.2    1877                                     V      20          2186      11.0    2085                                     ______________________________________                                    

EXAMPLES VI-X

Samples of glass fiber cord, G-75, 5/0 were sized with the followingcomposition:

    ______________________________________                                        Ingredient               Amount                                               ______________________________________                                        Versamide 140 (polyamino polyamide                                                                     26.9 pounds                                          condensation product of dimer acid                                            and a polyamine)                                                              Abraze-Ade (non-ionic emulsion of 12                                                                   389.8 pounds                                         percent polypropylene, 12 percent poly-                                       ethylene and 6 percent emulsion-stabilizer)                                   Alamine 7D (stearyl amine, cationic                                                                    2.7 pounds                                           surface active agent)                                                         Nalco D-2226 (acetate salt of the                                                                      8.2 pounds                                           condensation product of aminoethylethanolamine                                and hydrogenated tallow fat.                                                  A-1100 (gamma-aminopropyltriethoxysilane)                                                              15.3 pounds                                          Sag 470 (silicone anti-foam agent)                                                                     120 milliliters                                      Acetic acid              3300 milliliters                                     Sufficient water to make 300 gallons                                          ______________________________________                                    

The glass fibers were sized in accordance with the method described inU.S. Pat. No. 3,655,353, incorporated herein by reference and werecoated with the compositions of Examples I through V. The coating methodwas in accordance with the method described in U.S. Pat. No. 3,619,252,incorporated herein by reference.

According to the method of U.S. Pat. No. 3,619,252 a plurality of glassfiber strands each having a slight twist to provide strand integritywhich have been previously sized are combined in parallel relation andpassed through a guide in tangential contact across motor drivenrollers. The rollers are partially immersed in one of the coatingcompositions of Examples I through V and these rollers pick up thiscoating composition when rotated. The coating which is picked up isbrought into contact with the glass fiber strands, coating andimpregnating the combined bundle of strands. Relaxation of tension inthe combined bundle of strands opens the spacing between the fibers andbetween the strands enhancing impregnation of the coating compositioninto the bundle. The total impregnation is limited by the volumeavailable between the fibers and strands and by the volume of coatingsolids in the total dip volume which fills the voids in the bundle. Highsolids concentration in the dip is utilized when it is desired to obtainfull impregnation with the coating composition and not merely withwater. The coating composition solids were applied in order that thecords so formed would be composed of 30 percent of the dried coatingcomposition based on dry glass weight.

After coating the fiber glass bundle with a coating composition forsufficient time to fully impregnate the bundle with the water and solidscontaining composition, the bundle is passed through a dielectric heateror drying oven. The drying oven is so designed and operated that wateris removed rapidly from inside the bundle as well as from the surface ofthe bundle without substantial migration of the solids from the interiorto the surface of the bundle and without excessive blistering.

The dried glass fiber bundle is then subjected to heat to partially curethe rubber adhesive coating throughout the bundle. It is preferable topartially cure the coating while the coated fiber remains separate andto complete the curing of the coating on the glass fiber bundle when itis embedded in the rubber being reinforced during the curing of therubber in the final article.

Five series of glass fiber cord were made, each having the sizingcomposition previously described and each set having a different coatingcomposition, those being of Examples I through V.

From these glass fiber cords, five series of tires were made and testedby mounting the tires on an automobile and running the automobile over acobblestone test track. Periodically the test was interrupted and thetires were X-rayed to determine the breakage of the individual filamentsin the tire cord. The following table represents the performance of thecords coated with compositions of Examples I through V:

                  Table 2                                                         ______________________________________                                        Example          Laps Per First 50 Breaks                                     ______________________________________                                        I                 480                                                         II                120                                                         III              2160                                                         IV               4920                                                         V                8400                                                         ______________________________________                                    

Thus it can be seen from the combined data of Table 1 and 2 that thequantitative improvement in the performance of cord in a reinforcedarticle is proportional to various properties of a free film of thecoating composition. Therefore the films of the instant inventionprovide a means for economical testing of glass fiber coatingcompositions to correlate with how glass fibers with these coatingcompositions will perform in reinforced elastomeric articles.

While the present invention has been described with reference toparticular perferred embodiments, it will be appreciated by thoseskilled in the art that variations may be employed without departingfrom the spirit of the invention and the invention is only to be limitedinsofar as set forth in the accompanying claims.

We claim:
 1. In the method of testing an aqueous admixture of a coatingcomposition to be used for coating glass fibers used to reinforceelastomers, the improvement comprising:spraying an amount of saidadmixture onto a surface, said surface being at a temperature greaterthan 120° F., the amount of said admixture forming a base film of lessthan about 0.7 mil thickness, the adhesion between said surface and saidfilm being less than the cohesion within said film; spraying a pluralityof additional coats of said admixture over said base film, each of saidadditional coats imparting a coat thickness of less than about 0.7 mil,to form a continuous, uniform final film of greater than 4 milsthickness which is substantially water free, removing said final filmfrom said substrate; heating said final film with pressure to cure saidfilm; preparing test samples from said film; and testing said sample forstrength and percent elongation.
 2. The method of claim 1 wherein saidaqueous admixture contains 15 to 50 percent total solids by weight. 3.The method of claim 1 wherein said final film has a thickness of 4 to 23mils.
 4. The method of claim 1 wherein said surface is composed of anonadherent fluoropolymer.
 5. The method of claim 1 wherein said latexis a styrene-butadiene-vinylpyridine latex.
 6. The method of claim 1wherein said phenolic resin is a resorcinol-formaldehyde resin.
 7. Themethod of claim 1 wherein said film is cured at about 300° F. and 1,000pounds per square inch.